Organoleptic compounds and their use in perfume compositions

ABSTRACT

The present invention is directed to the novel compounds of the general formula 
     
       
         
         
             
             
         
       
     
     wherein R represents hydrogen or a straight, branched or cyclic hydrocarbon moiety consisting of less than 15, preferably less than 10, most preferably less than 4 carbon atoms and containing at least one oxygen atom and single and/or double bonds.

STATUS OF RELATED APPLICATIONS

This application is a divisional of U.S. Ser. No. 11/376,385, filed Mar.15, 2006, the contents hereby incorporated by reference as if set forthin its entirety.

FIELD OF THE INVENTION

The present invention relates to new chemical entities and theincorporation and use of the new chemical entities as fragrancematerials.

BACKGROUND OF THE INVENTION

There is an ongoing need in the fragrance industry to provide newchemicals to give perfumers and other persons the ability to create newfragrances for perfumes, colognes and personal care products. Those withskill in the art appreciate how differences in the chemical structure ofthe molecule can result in significant differences in the odor, notesand characteristics of a molecule. These variations and the ongoing needto discover and use the new chemicals in the development of newfragrances allow the perfumers to apply the new compounds in creatingnew fragrances.

SUMMARY OF THE INVENTION

The present invention provides novel chemicals, and the use of thechemicals to enhance the fragrance of perfumes, toilet waters, colognes,personal products and the like. In addition, the present invention isdirected to the use of the novel chemicals to enhance fragrance inperfumes, toilet waters, colognes, personal products and the like.

More specifically, the present invention is directed to the novelcompounds represented by Formula I set forth below:

wherein R represents hydrogen or a straight, branched or cyclichydrocarbon moiety consisting of less than 15, preferably less than 10,most preferably less than 4 carbon atoms and containing at least oneoxygen atom and single and/or double bonds.

In another embodiment, the present invention is directed to the novelcompounds represented by the general Formula II set forth below:

wherein R¹ represents hydrogen or a straight, branched or cyclichydrocarbon moiety consisting of less than 15, preferably less than 10,most preferably less than 4 carbon atoms and containing single and/ordouble bonds.

Another embodiment of the invention is directed to a method forenhancing a perfume composition by incorporating an olfactory acceptableamount of the compounds provided above.

These and other embodiments of the present invention will be apparent byreading the following specification.

DETAILED DESCRIPTION OF THE INVENTION

In Formulas I and II above, R and R¹ independently represent hydrogen ora straight, branched or cyclic hydrocarbon moiety consisting of lessthan 15, preferably less than 10, most preferably less than 4 carbonatoms and containing single and/or double bonds. Suitable straighthydrocarbon moieties include ethyl, propyl, butyl, pentyl, hexyl, andthe like. Suitable branched hydrocarbon moieties include isopropyl,sec-butyl, tert-butyl, 2-ethyl-propyl, and the like. Suitablehydrocarbon moieties containing double bonds include ethene, propene,1-butene, 2-butene, penta-1-3-deine, hepta-1,3,5-triene and the like.Cyclic hydrocarbons include cyclopropyl, cyclobutyl, cyclohexyl, phenyland the like.

In another embodiment of the invention, the novel compounds of theinvention are represented by the following structures:

Those with the skill in the art will appreciate that the compound ofStructure I is 1,2 Dihydro-Ethyl Linalool; Structure II is 3-Nonene,7-Methoxy-3,7-Dimethyl; Structure III is 6-Nonen-3-ol3,7-Dimethyl-Acetate; Structure IV is 3-Nonene,3,7-Dimethyl-7-[(2-Methyl-2-Propenyl)Oxy]-; and Structure V is3-phenyl-acrylic acid 1-ethyl-1,5-dimethyl-hept-4-enyl ester.

The compounds of the present invention may be prepared from thecorresponding compounds via a catalyzed hydrogenation reaction of thefollowing sequence:

The starting materials for the above reaction are commercially availablefrom Kuraray Chemical Company. Those with skill in the art willappreciate the following catalyst reagents abbreviated as Pd/C ispalladium on active carbon, Ac₂O is acetic anhydride, MSA ismethanesulfonic acid, NaH is sodium hydride, CH₃I is methyl iodide, THFis tetrahydrofuran and HMPA is hexamethylphosphoric triamide.

Those with skill in the art will recognize that some of the compounds ofthe present invention have a number of chiral centers, thereby providingnumerous isomers of the claimed compounds. It is intended herein thatthe compounds described herein include isomeric mixtures of suchcompounds, as well as those isomers that may be separated usingtechniques known to those having skill in the art. Suitable techniquesinclude chromatography such as high performance liquid chromatography,referred to as HPLC, and particularly gel chromatography and solid phasemicroextraction, referred to as SPME.

We have discovered that the fragrance compound of Structure I has fresh,floral, muguet, citrus, clean, coriander and bergamot notes. StructureII has strong, linalool, spicy, oregano, green, guava, woody,dihydromyrcenol, citrus, lime and herbal fragrance notes. Structure IIIhas soft, milder, green, dihydromycenol citrus, lime, herbal and woodyfragrance notes. Structure IV has strong, cleaner, linalool, less greenguava, fruity, dihydromyrcenol citrus, lime and herbal fragrance notes.Structure V has strong, balsamic sweet, floral and spicy fragrancenotes.

The use of the compounds of the present invention is widely applicablein current perfumery products, including the preparation of perfumes andcolognes, the perfuming of personal care products such as soaps, showergels, and hair care products as well as air fresheners and cosmeticpreparations. The present invention can also be used to perfume cleaningagents, such as, but not limited to detergents, dishwashing materials,scrubbing compositions, window cleaners and the like.

In these preparations, the compounds of the present invention can beused alone or in combination with other perfuming compositions,solvents, adjuvants and the like. The nature and variety of the otheringredients that can also be employed are known to those with skill inthe art.

Many types of fragrances can be employed in the present invention, theonly limitation being the compatibility with the other components beingemployed. Suitable fragrances include but are not limited to fruits suchas almond, apple, cherry, grape, pear, pineapple, orange, strawberry,raspberry; musk, flower scents such as lavender-like, rose-like,iris-like, carnation-like. Other pleasant scents include herbal andwoodland scents derived from pine, spruce and other forest smells.Fragrances may also be derived from various oils, such as essentialoils, or from plant materials such as peppermint, spearmint and thelike.

A list of suitable fragrances is provided in U.S. Pat. No. 4,534,891,the contents of which are incorporated by reference as if set forth inits entirety. Another source of suitable fragrances is found inPerfumes, Cosmetics and Soaps, Second Edition, edited by W. A. Poucher,1959. Among the fragrances provided in this treatise are acacia, cassie,chypre, cyclamen, fern, gardenia, hawthorn, heliotrope, honeysuckle,hyacinth, jasmine, lilac, lily, magnolia, mimosa, narcissus, freshly-cuthay, orange blossom, orchid, reseda, sweet pea, trefle, tuberose,vanilla, violet, wallflower, and the like.

Olfactory effective amount is understood to mean the amount of compoundin perfume compositions the individual component will contribute to itsparticular olfactory characteristics, but the olfactory effect of theperfume composition will be the sum of the effects of each of theperfumes or fragrance ingredients. Thus the compounds of the inventioncan be used to alter the aroma characteristics of the perfumecomposition, or by modifying the olfactory reaction contributed byanother ingredient in the composition. The amount will vary depending onmany factors including other ingredients, their relative amounts and theeffect that is desired.

The level of compound of the invention employed in the perfumed articlevaries from about 0.005 to about 10 weight percent, preferably fromabout 0.5 to about 8 and most preferably from about 1 to about 7 weightpercent. In addition to the compounds other agents can be used inconjunction with the fragrance. Well known materials such assurfactants, emulsifiers, polymers to encapsulate the fragrance can alsobe employed without departing from the scope of the present invention.

Another method of reporting the level of the compounds of the inventionin the perfumed composition, i.e., the compounds as a weight percentageof the materials added to impart the desired fragrance. The compounds ofthe invention can range widely from 0.005 to about 70 weight percent ofthe perfumed composition, preferably from about 0.1 to about 50 and mostpreferably from about 0.2 to about 25 weight percent. Those with skillin the art will be able to employ the desired level of the compounds ofthe invention to provide the desired fragrance and intensity.

The following are provided as specific embodiments of the presentinvention. Other modifications of this invention will be readilyapparent to those skilled in the art. Such modifications are understoodto be within the scope of this invention. As used herein all percentagesare weight percent unless otherwise noted, ppm is understood to standfor parts per million and g is understood to be grams. IFF as used inthe examples is understood to mean International Flavors & FragrancesInc., New York, N.Y., USA.

EXAMPLE A Preparation of 6-Nonen-3-ol, 3,7-Dimethyl-

1000 g of ethyl linalool (available from Kuraray Chemical Company) andPd/C were charged in an autoclave. The pressure reservoir was raised to1720 psi and then the autoclave pressure was held at 100 psi. Thereaction was sampled after two hours. The reaction mixture was cooledand allowed to settle. The layers were separated to provide6-nonen-3-ol, 3,7-dimethyl-.

The NMR of the 6-nonen-3-ol, 3,7-dimethyl- is as follows:

0.9 ppm (s, 3H); 1.0 ppm (s, 3H); 1.2 ppm (s, 3H); 1.4 ppm (m, 4H); 1.6ppm (m, 2H); 1.7 ppm (s, 2H); 2.0 ppm (m, 3H).

The compound was described to have fresh, floral, muguet, citrus, clean,coriander and bergamot fragrance notes.

EXAMPLE B Preparation of 3-Nonene, 7-Methoxy-3,7-Dimethyl-

To a dry 2 L multi-neck round bottom flask fitted with an air stirrer,nitrogen inlet condenser and an additional funnel, 400 ml of THF, 44 gof NaH, and 21.2 g of dihydroethyl linalool were added and heated to35-40° C. 170 g of dihydrolinalool g was then added to the reactionmixture dropwise over 2 hours. The mixture was aged for 8 hours. 9 g ofHMPA (available from Aldrich Chemical Company) was added and the mixturewas stirred. 144 g of CH₃I was added dropwise to the reaction mixture,further aged for two hours and then sampled hourly until maximumconversion was reached. The mixture was cooled and 800 ml of 5% HClsolution was added, allowed to settle, and the organic layer wasseparated. The aqueous layer was extracted with 3×100 ml of toluene andthen dried over MgSO₄ to provide 3-nonene, 7-methoxy-3,7-dimethyl-.

The NMR of the 3-nonene, 7-methoxy-3,7-dimethyl- is as follows:

0.9 ppm (m, 3H); 1.3 ppm (s, 6H); 1.4-1.5 ppm (m, 2H); 2.0 ppm (m, 2H);2.1 ppm (s, 3H); 4.5 ppm (s, 2H); 4.9 ppm (s, 1H); 5 ppm (s, 1H).

The compound was described to have strong, linalool, spicy oregano,green guava, woody, dihydromyrcenol citrus, lime and herbal fragrancenotes.

EXAMPLE C Preparation of 6-Nonen-3-ol, 3,7-Diemthyl-Acetate-

To a dry 2 L multi-neck round bottom flask fitted with an air stirrer,nitrogen inlet condenser and an additional funnel, 400 ml of toluene,0.48 g of MSA and 85 g of dihydroethyl linalool were added and stirredat room temperature. 102 g of acetic anhydride was added dropwise andthe temperature was maintained at 30° C. The reaction mixture wassampled hourly until maximum conversion. Water was then slowly addeduntil the acetic anyhydride was decomposed. The contents were washedwith cold water, 5% NaOH, and then with brine. The crude wasconcentrated to give the product.

The NMR of the 6-nonen-3-ol, 3,7-diemthyl-acetate- is as follows:

0.9 ppm (s, 3H); 1.0 ppm (s, 3H); 1.4 ppm (d, 3H); 1.6 ppm (m, 3H); 1.8ppm (m, 2H); 1.9 ppm (m, 1H); 2.0 ppm (m, 2H).

The compound was described to have soft, milder, green, dihyromycenolcitrus, lime, herbal and woody fragrance notes.

EXAMPLE D Preparation of 3-Nonene,3,7-Dimethyl-7-[(2-Methyl-2-Propenyl)oxy]-

To a dry 2 L multi-neck round bottom flask fitted with an air stirrer,nitrogen inlet condenser and an additional funnel, 200 ml of THF, 50 gof sodium hydride and 300 ml of THF were added and stirred. The mixturewas then heated to reflux. 170 g of dihydroethyl linalool was addeddropwise over a 1 hour period. The mixture was then aged for 8 hours. 5g of NaI and 9 g of hexamethylphosphoramide (HMPA) were added to themixture and heating was resumed. 110 g of methallyl chloride was addeddropwise to the mixture. The product was isolated after usual work up.

The NMR of the 3-nonene, 3,7-dimethyl-7-[(2-methyl-2-propenyl)oxy]- isas follows:

0.9 ppm (s, 3H); 1.0 ppm (s, 3H); 1.1 ppm (s, 3H); 2.0 ppm (m, 4H); 3.7ppm (s, 2H); 4.8 ppm (s, 1H); 5.0 ppm (s, 2H); 5.1(m, 1H).

The compound was described to have strong, cleaner, linalool, less greenguava, fruity, dihydromyrcenol citrus, lime and herbal fragrance notes.

EXAMPLE E Demonstration Fragrance Formula with Ethyl Dihydrolinalool

DESCRIPTION PARTS BACDANOL BHT 1.00 ETHYL DIHYDROLINALOOL 10.00 ALD AATRIPLAL BHT 10% DEP 0.50 ALD C-11 ULENIC UB BHA 10% DEP 0.20 MENTHOLCRYST USP NAT 0.50 CYCLOGALBANIFF BHT 10% DEP 0.50 METH SALICYLATE 0.10BENZYL ACETATE 5.00 BENZYL SALICYLATE 4.00 CINN ALCOHOL 2.00 GALAXOLIDE50 PCT DEP 6.00 HELIOTROPINE (PIPERONAL) (USDEA) 5.00 PHEN ETH ALC WHITEEXTRA 10.00 SANDALWOOD OIL INDIA RECT LMR 2.00 SANTALIFF BHT 5.00VERTOFIX COEUR 2.00 ACALEA BHT/BHA 2.00 HYDROXYCIT EXTRA 3.00 LILIAL4.00 LYRAL BHT 7.00 VANILLIN EX LIGNIN 2.00 DIPROPYLENE GLYCOL 26.20 ISOE SUPER BHT 2.00 TOTAL: 100.00

The ethyl dihydrolinalool provided a more floral and more diffusive noteto the fragrance formulation.

1. A compound of formula

wherein R¹ represents hydrogen or a straight, branched or cyclichydrocarbon moiety consisting of less than 15 carbon atoms andcontaining single and/or double bonds.
 2. The compound of claim 1,wherein R¹ represents a straight, branched or cyclic hydrocarbon moietyconsisting of less than 10 carbon atoms.
 3. The compound of claim 1,wherein R¹ represents a straight, branched or cyclic hydrocarbon moietyconsisting of less than 4 carbon atoms.
 4. A method of improving,enhancing or modifying a fragrance formulation through the addition ofan olfactory acceptable amount of the compound of claim
 1. 5. The methodof claim 4, wherein the fragrance formulation is incorporated into aproduct selected from the group consisting of a perfume, a cologne,toilet water, a cosmetic product, a personal care product, a fabric careproduct, a cleaning product, and an air freshener.
 6. The method ofclaim 5, wherein the cleaning product is selected from the groupconsisting of a detergent, a dishwashing composition, a scrubbingcompound, and a window cleaner.
 7. The method of claim 4, wherein theolfactory acceptable amount is from about 0.005 to about 10 weightpercent.
 8. The method of claim 4, wherein the olfactory acceptableamount is from about 0.5 to about 8 weight percent.
 9. The method ofclaim 4, wherein the olfactory acceptable amount is from about 1 toabout 7 weight percent.
 10. A fragrance formulation containing acompound of formula

wherein R¹ represents hydrogen or a straight, branched or cyclichydrocarbon moiety consisting of less than 15 carbon atoms andcontaining single and/or double bonds.
 11. A fragrance productcontaining a compound of formula

wherein R¹ represents hydrogen or a straight, branched or cyclichydrocarbon moiety consisting of less than 15 carbon atoms andcontaining single and/or double bonds.